Process eob tee erodttoraon of alcohol ekom gas c



UNITED STATES CLEBU'RNE A. BASORE, OF AUBURN, ALABAMA.

PROCESS FOR THE PR GDUGTION 0F No Drawing,

To all whom it may concern:

Be'it known that I, CLEBURNE A. BAsoRn, a citizen of the United States of America, residing at Auburn, in'the county of Lee and State of Alabama have invented certain new and useful Improvements in Processes for the Production of Alcohol from Gas Containing Ethylenaof which the following is a specification.

This invention relates to a novel process for the production of alcohol from by-product coke oven gas or other gascontaining ethylene, the tar, ammonia and light oil of which has primarily been removed during thilplant process in which gas is made.

' y invention contemplates the preliminary treatment of the gas so as to remove therefrom the hydrogen sulfid, water and preferably the carbon dioxid and it is then '20 volume of water added to the ethyl hydrogen sulfate. H

scrubbed by causing it to bubble through hot concentrated sulfuric acid to produce ethyl hydrogen sulfate as a resultant compound in the scrubbers while the gases pass off to the servic'emains for commercial use, practically unaffected by the removal therefrom of the ethylene: The ethyl hydrogen sulfate is then admixed with a predetermined and definite quantity of water, which is restricted to the proportions necessary for the contemplated reactions andno more. The resultant mixture is then subjected to heat in a suitable closed apparatus which will maintain for a predetermined length of time the requisite temperature conditions for the uniting of the oxygen and hydrogen in the water with the C 7 5 of the ethyl hydrogen I sulfate to form alcohol and when this reaction is substantially complete, which requires approximately one hour, the resultant prod uctis distilled and condensed in any well known manner and the alcohol recovered, the extent ;.to which it is diluted being controlled arid limited by the control of the which length of time'is preferably obtained under proper conditions by heating the mix ture of water and ethyl hydrogen sulfate in a closed vessel under a temperature ref- 'erably ranging between 100and 120 In my experiments I have found that the reaction in which the OH from the water unltes with 0 H; in the ethyl hydrogen sulfate I Application filed. March 14,

, produce 'C I-I OII (alcohol) is one that Specification of Letters Patent i Patented July 26 a 1921. Serial mi. 452,285.

develops rather slowly and to obtain the ALCOHOL FROM GAS CONTAINING ETHYLIENE.

maximum production of alcohol it is essential that this reaction shall have ample time to proceed to a finish. Bearing in mind that it must be conducted in the presence of heat, I have concluded that the most practical way to complete the reaction is in a vessel where the desired temperature conditions can be maintained indefinitely, should it benecessary. I have determined by experiment thatthe reaction under a temperature of approximately 110'? C.-is ordinarily com- \pleted in from to minutes. When the reaction has been thus completed the finalstep of distlllation and condensation for the recovery of the alcohol and for the recovery of the sulfuric acid for reuse in the scrubbers, can proceed in any well known manner.

As a result of the control oi the reaction in question, I am enabled to obtain the maxi-Q mum alcohol output from the original constituents.

Another distinctive feature of my invention is based upon the control'and definite limitation of the volume of water added to the ethyl hydrogen sulfate. Heretofore it has been attempted to treat ethyl hydrogen sulfate with steam, and alcohol to a limited extent has been obtained in this manner, but the process has never gone into general use because the requisite time for the completion of the reaction was not provided for and there was no control or limitation of the volume of water added in the form of steam and as a result of the-latter fact the relatively smal-lvolume of alcohol recovered volume of water, which may vary in the limits between 50 and70 per cent of the combined volume of ethyl hydrogen sulfate and sulfuric acid is added. Usually 60 per cent. in *volume ofwater to the other ele ments, 'will produce the most satisfactory operating results I have also discovered that when the degree of concentration of the ethyl hydrogen sulfate in the scrubbers is permitted to excfeed 30 per cent. by weight of thesulfuric acid in the scrubbers, then the subsequent dilution-and treatment 'of such .'concentr ated ethyl hydrogen sulfate in the' iclosedvessel was greatly diluted, as was also the residual Q5 and trouble, whereas by my process a definite will produce ether in substantial. quantity which will increase as the concentration of the ethyl hydrogen sulfate increases. 1 prefer to draw off the acid and ethyl hydrogen sulfate for my proposed treatment when the ethy hydrogen sulfate reaches a concentra- Lion of between 10 per cent. and 20 per cent.

by weight of the sulfuric acid.

in describing my process from the initial stage, utilizing by-product coke oven gas free from tar, ammonia and light oil, as a source of ethylene, reference is made to the drawings which illustrate a typical apparatus to which this gas, in accordance with well known practice, after being freed of its'hydrogen sulfid, water and preferably its carbon dioxid, is presented in heated condition (60 to centigrade) through a pipe or conduit 1 and enters either end scrubber of a series of scrubbers 2 which are charged with concentrated sulfuric acid and filled with broken particles 3 of inert matter such as coke, rock, etc. lhe gas which is under pressure is caused to bubble up through the tanks passing therethrough in series and the tanks are heated by any suitable burner equipment a or by superheated steam in chamber 5. The principal of counter-currents is used in the scrubbing. From the final scrubber the coke oven gas, freed of its ethylene, passes through the conduit 6 from the end scrubber of the series under control of its respective valve (i to the service main, while the ethyl hydrogen sulfate formed by absorption of ethylene in concentrated hot sulfuric acid (66 B. preferably heated to 70 to C.) is drawn off from the first scrubber, or any combination as first and second, through one of the pipes 8 and conducted past a valve 9 in each 'pipe 8 into a heating vessel 10 which is typically illustrated and may be of any suitable type. After drawing the ethyl hydrogen sulfate and sulfuric acid from a scrubber, the latter is then refilled with acid and made the last of the series. This heating vessel is preferably heated by side burners 11 surrounding the same opposite the liquid level therein and has a small amount of broken glass or inert particles 12 therein. These particles and the side burners are especially employed for preventing the foaming of the reacting liquids in the apparatus. A condensing coil 13 is connected by a pipe 14 to the top of the vessel 10 and is controlled by a valve 15. This condenser coil discharges into a collecting funnel 16 which is adapted to collect the recovered alcohol. A pipe 17 is used to conduct the sulfuric acid from the vessel 10 under control of valve 18 into filter 19, whence the liquid passes by a pipe 20 to an evaporating pan 21. Superheated steam for the purpose of steaming residual sulfuric acid is supplied to the vessel 10 by means of a pipe 22 under control of .valve 23, and

teasers water is supplied to said vessel through pipe as under control .of valve 25.

l l hen the ethyl hydrogen sulfate has reached the desired degree of concentration in the sulfuric acid (10% to 20% by weight thereof) it is ready for treatment in the heating vessel 10 and it is delivered theret through one or more pipes 8 by opening their respective valves 9, the valves 15, 18, 23 and 25 being previously closed and the valves 9 being closed after the admission of the ethyl hydrogen sulfate and sulfuric acid. The water in volume approximately 00 1 cent. of the volume of ethyl hydrogen fate and sulfuric acid then supp through water pipe 24- and the ii is lighted and the refluxin trea 1c cone mences and is continued for approximately 60 minutes under temperatures of the liquid ranging from to 120 0., during which treatment the liquids within the ap paratus are being continuously volatilized and condensed and the reaction is proceeding in accordance with the following equation:

e ress0 +nonzo n on n so The uniting of OH with C H to form alcohol takes place slowly and hence is best accomplished in a closed heating apparatus for the requisite time before commencing the distilling and condensing operations. At the completion of the reaction, valve 15 to the coil is opened and the vapors, consisting of alcohol, water and some sulfur dioxid, pass through the coil and the alcohol and water are condensed until all of the available alcohol is recovered. The sulfur dioxid gas, largely uncondensed, may be used for removal of the hydrogen sulfid from the raw gas,

or it can be recovered by absorption in a water tank 30 or by liquefaction. After this live steam can be admitted through pipe 22 in sufiicient volume to coagulate the colloids in the remaining sulfuric acid and the latter can then be drained off through the filter and thereby relieved of its foreign matter except the water which is removed in the evaporating mechanism 21. The resultant product is substantially pure acid. The alcohol with its surplus water content and sulfur dioXid is then treated in any Well known manner for the elimination of the water and sulfur dioxid and the resultant product is pure commercial alcohol.

I have also found that the'successful operation of the process is dependent upon the slow and uniform feed of the gases to the scrubbers; any suitable regulating means, as valve 26, being provided to feed it slowly enough to effect the substantial removal of the ethylene in the scrubbers. Care should lied.

also be taken 'to keep the concentration of. ethyl hydrogen sulfate in the sulfuric acid in the scrubbers below '30 per cent. by weight to the endthat the percentage ma not rise high enough to produce ether. Vlhile the figures which I have given for volume of water added and for the time of the reaction in the heating apparatus 10 are those which -my experiments have found to be most satisfactory, it is, nevertheless, to be understood that these may be varied Within the,

scope of my invention and with approximate results proportionate to the departure from those figures and proportions which I have found most suitable.

This application is a continuation in part of my application Serial No. 417,224, filed October 15th, 1920'. I Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is

l. The hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate,

which consists in adding to said mixture water in excess of 50 per cent. of the volume of said mixture, subjecting the resultant reacting constituents to heat in a closed vessel, then distilling off the alcohol and water, and finally condensing thealcohol.

2. The hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate,

.which consists in adding to said mixturev water in amount equal to from 50 per cent. to per cent. of the volume of the said mixture, subjecting the resultant reacting constituents to heat in a closed vessel, then distilling off the alcohol and water, and finally-condensing the alcohol.

3. The hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate, which consists in adding to said mixture water in amount equal to approximately 6Ov per cent. of the volume of thesa'id mixture, subjecting the resultant reacting constituents to heat in a closed vessel, then distilling off the alcohol and water, and finally 'condensing the alcohol. j

4-. The herein'described process for the production of ethyl alchol from a mixture of sulfuric acid and ethyl hydrogen sulfate,

which consists in adding to said. mixture water in excess of 50 per cent. of the volume .of said mixture, subjecting the resultant reacting constituents to heat in a vessel. ocontinuously volatilize and recondens 5-. therein until the combination of (LB "HSO' with. HOH is substantially complete, then distilling off the alcohol and water, and finally condensin thejalcoh'ol.

5. The herein escribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate,

of the ethyl acid, subjecting the reacting .mi'xture'to heat which consists in adding to said mixture water in excess lof 50 per cent. of the volume of said mixture, subjectingthe resultant reacting constituen'ts to heat in a vessel to continuously volatilize and recondense them therein for approximately 60 minutes, then distilling off the alcohol and water, and

condensing the alcohol.

finally 6. he hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate,

production of alcohol from'gas containing ethylene, which consists in treating the gas with hot concentrated sulfuric ac1d66 B. 7 0 to 80 C. to form ethyl hydrogen sulfate not in excess of .30 per cent. in weight of the acid in the mixture, addin g to the ethylhydrogen sulfate and sulfuric acid a volume of combined volume, treating the resultant;

com ound in a'closed heating-apparatus an: 1

lie reaction involving the unitin of the hydroxyl radical with the O,H 'in t e ethyl til t hydrogen sulfate to form alcohol is practically completed, then distilling offhand condensing thevalcohol. v

8. The hereindescribed roduction of alcoholethylene bearing-gas "me of tar, ammonia and light oil, hydrogen sulfid, water, and pre erably carbon .dioxid, which consists in treating the with hot concentrated sulfuric acid ,66' B. 7 0 to 80 C. until the concentration of ethyl hydrogen sulfate in the sulfuric acid has reached a degree of from 10 per cent. to 20 percent. by wei 'ht of the acid in said mixture, drawing 0 the ethyl hydrogkegl sulfage ers, a

and sulfuric acid from the scru mixing with the latter an amount of water approximatel 60 per cent. of the volume ydrog'en sulfate and'sulfuric water approximately (50 per ce'ntJof their" 1 4 the of from 100 to C. for approximately"- an hour in a vessel adapted to continuously yolatilize and recondense it therein, and

tilling off and condensing the, alcothen hol,s1i tantially as described.

9. hereindescribed. rocess of sulfuric acid and ethyl hydrogen sulfate, which consists in adding water to said mix- I for the" production of j ethyl alcoho from a mixture ture in volume not less than 5.0(Fer cent. of

the volumeof the mixture,hol ng the resultantimixture under heat inia vessel until the c'ombinatio n of C,H,HSO, with HOH rag is substantially complete, and then distilling off and condensing dilute alcohol.

10. The hereindescribed process for the production of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen. sulfate, Which consists in adding Water to said mixture in volume between 50 and 70 per cent. of the volume of the I11lXtl1I6,l10ldlllg the resultant mixture under heat until the hydroxyl radical has combined With the C ll radical, and then distilling oil and condensing dilute alcohol.

11. The hereindes'cribed process for the production. of ethyl alcohol from a mixture of sulfuric acid and ethyl hydrogen sulfate 15 in which the latte is less than 30 per cent. by weight of the former, which consists in adding Water to said mixture in volume not less than 50 per cent. of the volume of the mixture, holding the resultant mixture under heat in a vessel until the combination of U H HSU. with HUI-l. is substantially complete, and then distilling elf and condensing dilute alcohol.

in testimony whereof I affix my signature. 25

ULEBUR NE A. BASUPM /Fitness H v Nome Withers. 

